CN105013527B - Core-shell structured Beta molecular sieve and preparation method thereof - Google Patents
Core-shell structured Beta molecular sieve and preparation method thereof Download PDFInfo
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- CN105013527B CN105013527B CN201510366545.9A CN201510366545A CN105013527B CN 105013527 B CN105013527 B CN 105013527B CN 201510366545 A CN201510366545 A CN 201510366545A CN 105013527 B CN105013527 B CN 105013527B
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000011258 core-shell material Substances 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000013049 sediment Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 240000001414 Eucalyptus viminalis Species 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 abstract 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- 238000005119 centrifugation Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 diallyl dimethyl ammoniumchlorides Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229950000845 politef Drugs 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
A core-shell structured Beta molecular sieve comprises 70-75wt% of an inner layer Beta molecular sieve core structure and 25-30wt% of an outer layer Beta molecular sieve shell structure wrapped outside the surface of the core structure, total silicon Beta molecular sieve is adopted as the carrier of the inner layer Beta molecular sieve to support copper and/or iron oxide, the copper and/or iron oxide accounts for 3-8% of the mass of the total silicon Beta molecular sieve, the surface of the inner layer Beta molecular sieve is connected with a poly(diallyldimethylammonium chloride) group, and 10-15% of nickel oxide is supported on the outer layer Beta molecular sieve. The core-shell structured Beta molecular sieve utilizing synergism of inner and outer double-layer molecular sieves and supported metal elements has high catalysis activity, and has the advantages of great improvement of the selectivity of a target product hydrogen, and very high ethanol conversion rate and hydrogen selectivity as an ethanol steam reforming hydrogen production catalyst.
Description
Technical field
The present invention relates to Beta molecular sieves, more particularly to a kind of Beta molecular sieves with nucleocapsid structure, and it is described
The preparation method of Beta molecular sieves.Different metal active constituents are loaded with the Beta molecular sieve nucleocapsid structures of the present invention, can
As the catalyst application of catalyzing manufacturing of hydrogen.
Background technology
Since 21 century, people increasingly increase the demand of the energy, and exploitation novel renewable energy, clean energy resource become
The inexorable trend of future source of energy development.In numerous regenerative resources, Hydrogen Energy is considered as that a kind of cleaning of most potential quality is replaced
For the energy.
The preparation of hydrogen is presently mainly carried out by methane vapor reforming method and water electrolysis method, its course of reaction is adjoint
The generation of great amount of carbon dioxide, has surmounted environment and the balance of carbon dioxide has been limited, and causes the generation of greenhouse effect.Therefore, grind
The production that study carefully carries out hydrogen using renewable material has the advantage that can not be substituted, and the carbon dioxide produced during hydrogen is produced
Also it is capable of achieving the secondary utilization of conversion and cycle.Hydrogen production by ethanol steam reforming is the focus that for many years research worker is paid close attention to always, but
It is that the efficient ethanol hydrogen production catalyst of exploitation is also in conceptual phase.
The research of hydrogen production by ethanol steam reforming catalyst both at home and abroad is concentrated mainly at present to oxide carried transition gold
The report of category or noble metal type catalysis material.Research shows that the catalytic performance of catalyst depends on active component property, precursor
The each side such as type, preparation method, kind of carrier and additive, wherein carrier have for preparation high catalytic performance catalyst
Highly important effect：Carrier is favorably improved the dispersion of active component；By increasing the work between carrier and active component
Firmly, the sintering in course of reaction can be reduced, catalytic effect is improved；Carrier specific surface area increases, and can effectively improve catalysis
The catalysis activity of agent.
Molecular sieve due to the framing structure of itself uniqueness, high adsorption and bigger serface, as a kind of catalytic carrier material
Material will have broad application prospects.Campos-Skrobot etc. is anti-as ethanol steam reforming using NaY type molecular sieves first
Catalyst is answered, higher hydrogen selective is shown, but conversion ratio is relatively low, and reaction is incomplete.Chica etc. is by layer molecule
Sieve (ITQ-2 and ITQ-18) carried metal Ni and Co is used as catalyst, compared with conventional oxide carrier load type catalyst, table
Reveal more preferable catalytic performance, but by-product is more in course of reaction, the easy carbon distribution inactivation of catalyst.
It is the most obvious with the catalysis advantage of Ni, Cu and Fe in the active component of hydrogen production by ethanol steam reforming catalyst.Ni
With very strong disconnected C-C bond energys power, but for H2Selectivity it is poor；Cu has disconnected O-H bond energy power well, H2Yield but
It is very low；Fe has good catalytic performance, but weaker for the transfer capability of ethanol.Up to the present, it is relevant both at home and abroad to divide
The patent and quantity of document that son sieve loaded catalyst is applied to hydrogen production by ethanol steam reforming reaction is less, and is mainly limited to
Single molecular sieve is carrier and loads the catalytic performance research of single metal active constituent catalyst.
The content of the invention
It is an object of the invention to provide a kind of nucleocapsid structure Beta molecular sieves and preparation method thereof, a kind of with double to provide
Rotating fields and various active component, it is adaptable to the catalyst of hydrogen production by ethanol steam reforming.
The nucleocapsid structure Beta molecular sieves that the present invention is provided are by inner layer B eta molecular sieve nuclear structure, and are wrapped in the core
The outer layer Beta molecular sieves shell structure composition of body structure surface, wherein inner layer B eta molecular sieve nuclear structure accounts for nucleocapsid structure Beta molecules
70～75wt% of sieve, outer layer Beta molecular sieve shell structures account for 25～30wt%.
The inner layer B eta molecular sieve is loaded with accounting for the total silicon Beta molecular sieve supported with total silicon Beta molecular sieves as carrier
The copper and/or iron oxides of weight 3～8%, and it is connected with diallyl dimethyl chlorination in inner layer B eta molecular sieve surface
Ammonium group.
The outer layer Beta molecular sieves by Beta molecular sieve carriers, and be carried on it is on the carrier, account for carrier quality
10～15% nickel oxide is constituted.
The crystal grain diameter of nucleocapsid structure Beta molecular sieves of the present invention is 20～25 μm.
The preparation method of nucleocapsid structure Beta molecular sieves of the present invention is comprised the following steps：
1) according to the ratio of metal oxide supported 3～8wt% of amount in inner layer B eta molecular sieve, by total silicon Beta molecular sieves
Added with equi-volume impregnating with soluble copper salt and/or soluble ferric iron salt and be uniformly dispersed in ethanol, make ethanol fully volatilize, shape
Into inner layer B eta molecular sieve precursor, 500～550 DEG C of roastings obtain inner layer B eta molecular sieve；
2）Inner layer B eta molecular sieve is immersed and is fully acted in diallyl dimethyl ammoniumchloride, solid-liquid separation, solid
Thing obtains the inner layer B eta molecular sieve of pretreatment in 550～600 DEG C of roastings；
3) ratio of 70～75wt% is accounted for according to inner layer B eta molecular sieve in nucleocapsid structure Beta molecular sieves, successively by template
Agent tetraethyl ammonium hydroxide, inorganic silicon source, sodium hydroxide are added to the water to form transparent mixed solution, add Ludox, pre- place
The inner layer B eta molecular sieve of reason, stirring forms gel mixed solution, and 130～150 DEG C of hydro-thermal static crystallizations react 72～120h, Gu
Liquid is separated, and 550～600 DEG C of roastings obtain powder solid；
4) according to the ratio of metal oxide supported 10～15wt% of amount in outer layer Beta molecular sieves, by powder solid with can
Insoluble nickel salt is scattered in together in ethanol solution carries out incipient impregnation, makes ethanol fully volatilize, and forms nucleocapsid structure Beta point
Son sieve presoma, 500～550 DEG C of roastings obtain nucleocapsid structure Beta molecular sieves.
Wherein, described total silicon Beta molecular sieves are that template tetraethyl ammonium hydroxide and Ludox are dissolved in water into shape
Into clear solution, Deca Fluohydric acid. stirring and dissolving forms white gum mixed solution, by white gum mixed solution 130～160
120～240h of hydro-thermal static crystallization at DEG C；Separate solid sediment；It is dried to obtain white solid；550～600 DEG C of roastings obtain white
Color powder silica zeolite.
In above-mentioned preparation method, described soluble copper salt is copper nitrate, copper sulfate, copper bromide or copper chloride；Described
Soluble ferric iron salt is ferric nitrate, iron sulfate or iron chloride；Described soluble nickel salt is nickel nitrate, nickel sulfate, nickel sulfamic acid
Or Nickel dichloride..
Further, inner layer B eta molecular sieve is immersed and is fully acted in diallyl dimethyl ammoniumchloride by the present invention
Afterwards, solid-liquid separation, solidss are added to the water after being dried, and add the Beta molecular sieve seeds of a small amount of 50～100nm of particle diameter, and mixing is equal
It is even, solid-liquid separation, after solidss are dried, 550～600 DEG C of roastings obtain the inner layer B eta molecular sieve of pretreatment.
Wherein preferably, the addition of the Beta molecular sieve seeds accounts for the 3～6% of inner layer B eta molecular sieve quality.
Nucleocapsid structure Beta molecular sieves prepared by the present invention can be used as hydrogen production by ethanol steam reforming catalyst application.
The characteristics of present invention is based on catalyst with core-casing structure, using the functional characteristic and difference of different structure Beta molecular sieves
The catalysis advantage of metal active constituent, using two step hydrothermal crystallization methods, synthesizes the nucleocapsid for hydrogen production by ethanol steam reforming
Structure Beta molecular sieve catalyst, compensate for the defect of single molecular sieve type catalyst, by double-decker and various active group
Divide the yield for improving hydrogen, realize the efficient utilization of catalyst.
The present invention is with Ludox, sodium hydroxide, inorganic silicon source, tetraethyl ammonium hydroxide, soluble iron, copper, nickel salt, ethanol
Deng for raw material, diallyl dimethyl ammoniumchloride is inorganic agent, is reacted using hydrothermal crystallizing, first synthesizes inner layer B eta molecule
Sieve, after being processed internal layer Beta molecular sieves using inorganic agent, the Beta molecular sieves of resynthesis nucleocapsid structure.It is prepared by the present invention
20～25 μm of nucleocapsid structure Beta zeolite crystals diameter, internal layer molecular sieve outside little crystal grain parcel is tight, and product purity reaches
To 99.9%.
Using the nucleocapsid structure Beta molecular sieves of the present invention as hydrogen production by ethanol steam reforming catalyst, by inside and outside two-layer
Synergism between Beta molecular sieves and carried metal element, shows higher ethanol conversion and hydrogen selective, and
Byproducts of carbon monoxide, methane, the selectivity of formaldehyde are greatly reduced.
Description of the drawings
Fig. 1 is the X-ray diffraction intensity spectrogram of nucleocapsid structure Beta molecular sieves prepared by embodiment 1.
Fig. 2 is the SEM figures of nucleocapsid structure Beta molecular sieves prepared by embodiment 1.
Fig. 3 is the TEM figures of nucleocapsid structure Beta molecular sieves prepared by embodiment 1.
Specific embodiment
Embodiment 1
Ionized water 2mL, tetraethyl ammonium hydroxide 37.2mL are removed, Ludox 21.95mL adds together politef to hold
In device, 40 DEG C of stirring 3h are heated to, transparent mixed solution are formed, with the speed Deca Fluohydric acid. 2.88mL of 0.1mL/min, stirring
1h, forms white gum mixed solution.
The polytetrafluoroethylcontainer container that will be equipped with white gum mixed solution is put in stainless steel cauldron, closed, is placed in perseverance
In incubator, 140 DEG C of static crystallization 168h are heated to；Reactor is taken out, fast quickly cooling in 10 DEG C of deionized water is placed in quenching groove
But to 20 DEG C；By crystallization gel solution with 8000r/min centrifugation 20min, solid sediment is retained, be placed in vacuum drying oven
In, 100 DEG C are dried 12h, obtain white solid product.
White solid product after vacuum drying is placed in roaster, 550 DEG C of roasting 300min make the template in duct
Agent is fully deviate from, and obtains total silicon Beta molecular sieve white powder 6g.
White powder product 5g, copper nitrate 0.25g, ferric nitrate 0.24g are weighed, are added to together with ethanol 8mL in beaker,
Being placed in ultrasound wave separating apparatus carries out dissolving dispersion, frequency 59KHz, jitter time 60min.80 DEG C of constant temperature stirrings are heated to afterwards
6h, makes the volatile material in mixture fully volatilize, and forms inner layer B eta molecular sieve catalyst presoma.
Inner layer B eta molecular sieve catalyst presoma is placed in roaster, 500 DEG C of roasting 180min obtain inner layer B eta
Molecular sieve catalyst.
Weigh inner layer B eta molecular sieve catalyst 4g to add in 60mL diallyl dimethyl ammoniumchlorides, be stirred vigorously
1h, makes mixture fully act on, and forms mixed solution；8000r/min centrifugation 20min, retain solid sediment.By solid
Precipitate is placed in vacuum drying oven, and 100 DEG C are dried 12h, obtain white solid powder.
White solid powder 3g is weighed, Beta molecular sieve seeds 0.15g of 50～100nm of particle diameter add deionized water 40mL
In, 2h is stirred, Beta molecular sieve seeds is fully acted on white solid powder, form white mixed solution；5000r/min from
The heart separates 30min, retains solid sediment.Solid sediment is placed in evaporating dish, 100 DEG C of dryings in vacuum drying oven
12h, obtains pressed powder.
Dried pressed powder is placed in roaster, 550 DEG C of roasting 300min obtain pretreatment inner layer B eta molecule
Sieve catalyst.
Ionized water 0.77mL, tetraethyl ammonium hydroxide 0.96mL, aluminum sulfate 0.05g, sodium hydroxide 0.56g are removed, is added
To in polytetrafluoroethylcontainer container, stirring 3h forms transparent mixed solution；Take Ludox 1.52mL, pretreatment inner layer B eta molecular sieve
Catalyst 2g, in being added to transparent mixed solution, strong stirring 2h forms gel mixed solution.
The polytetrafluoroethylcontainer container for filling gel mixed solution is placed in it is closed in reactor, in being put into calorstat, heating
To 135 DEG C, constant temperature static crystallization reacts 72h；Take out, be placed in quenching groove, in 10 DEG C of deionized water 20 are quickly cooled to
℃；Mixed solution is poured in beaker, deionized water 1L, agitator treating 30min is added；3000r/min centrifugation 60min,
Retain precipitate.Washing, centrifugation repeat 3 times.
Precipitate after washing, centrifugation is placed in roaster, 550 DEG C of roasting 5h obtain white powder.
The white powder 2g after roasting, nickel nitrate 0.26g are weighed, is added together with ethanol 3.2mL in beaker, ultrasonic dissolved
Solution dispersion, frequency 59KHz, jitter time 60min；40 DEG C are heated to, constant temperature stirring 6h, agitation revolution 400r/min make mixing
Volatile material in thing fully volatilizees, and forms nucleocapsid structure Beta molecular sieve catalyst presomas.
Nucleocapsid structure Beta molecular sieve catalyst presomas are placed in into roaster, 500 DEG C of roasting 180min obtain nucleocapsid knot
Structure Beta molecular sieve catalysts sample 1.
Fig. 1 is the XRD spectra of sample manufactured in the present embodiment 1.Crystalline product material phase analysis are carried out with X-ray diffractometer,
Show that synthesized nucleocapsid structure Beta molecular sieve catalysts have the characteristic diffraction peak of Beta molecular sieves, without stray crystal, and deposit
In NiO, CuO, Fe2O3Characteristic peak, shows that synthesized nucleocapsid structure Beta molecular sieve catalysts have Beta molecular sieves and metal
Active component structure.
Nucleocapsid structure Beta molecular sieve catalysts manufactured in the present embodiment are white powder, and Fig. 2 is the SEM spectrograms of sample 1,
Crystalline product morphology analysis are carried out with scanning electron microscope, 20～25 μm of powder granule diameter is urged in inner layer B eta molecular sieve
The molecular sieve little particle of one layer of arranged regular is grown in agent, shows that synthesized sample has outside little crystal grain cladding internal layer point
The nucleocapsid structure of son sieve, structural integrity and shell parcel densification, are not physical mixed states.
Fig. 3 prepares the TEM spectrograms of sample 1 for the present embodiment, by the local with transmission electron microscope to sample crystal grain
Carry out product structure analysis to understand, in inner layer B eta zeolite crystal outer wrap the little crystal grain Beta molecule of one layer of densification
Sieve, this again shows that synthesized sample has nucleocapsid structure and clad structure is good.
Embodiment 2
Ionized water 2mL, tetraethyl ammonium hydroxide 37.2mL are removed, Ludox 21.95mL adds together politef to hold
In device, 40 DEG C of stirring 3h are heated to, transparent mixed solution are formed, with the speed Deca Fluohydric acid. 2.88mL of 0.1mL/min, stirring
1h, forms white gum mixed solution.
The polytetrafluoroethylcontainer container that will be equipped with white gum mixed solution is put in stainless steel cauldron, closed, is placed in perseverance
In incubator, 140 DEG C of static crystallization 168h are heated to；Reactor is taken out, fast quickly cooling in 10 DEG C of deionized water is placed in quenching groove
But to 20 DEG C；By crystallization gel solution with 8000r/min centrifugation 20min, solid sediment is retained, be placed in vacuum drying oven
In, 100 DEG C are dried 12h, obtain white solid.
White solid product after vacuum drying is placed in roaster, 550 DEG C of roasting 300min make the template in duct
Agent is fully deviate from, and obtains total silicon Beta molecular sieve white powder 6g.
White powder product 5g, copper nitrate 0.4g are weighed, is added to together with ethanol 5mL in beaker, be placed in ultrasonic wavelength-division
Dissolving dispersion, frequency 59KHz, jitter time 60min are carried out in scattered instrument.80 DEG C of constant temperature stirring 6h are heated to afterwards, make mixture
In volatile material fully volatilize, formed inner layer B eta molecular sieve catalyst presoma.
Inner layer B eta molecular sieve catalyst presoma is placed in roaster, 500 DEG C of roasting 180min obtain inner layer B eta
Molecular sieve catalyst.
Inner layer B eta molecular sieve catalyst 4g is weighed, in adding 50mL diallyl dimethyl ammoniumchlorides, is stirred vigorously
1h, makes mixture fully act on, and forms mixed solution；8000r/min centrifugation 20min, retain solid sediment.By solid
Precipitate is placed in vacuum drying oven, and 100 DEG C are dried 12h, obtain white solid powder.
White solid powder 3g is weighed, Beta molecular sieve seeds 0.1g of 50～100nm of particle diameter add deionized water 35mL
In, 2h is stirred, Beta molecular sieve seeds is fully acted on white solid powder, form white mixed solution；5000r/min from
The heart separates 30min, retains solid sediment.Solid sediment is placed in evaporating dish, 100 DEG C are dried 12h in vacuum drying oven,
Obtain pressed powder.
Dried pressed powder is placed in roaster, 550 DEG C of roasting 300min obtain pretreatment inner layer B eta molecule
Sieve catalyst.
Ionized water 0.84mL, tetraethyl ammonium hydroxide 0.75mL are removed, aluminum sulfate 0.12g, sodium hydroxide 0.48g adds poly-
In tetrafluoroethene container, stirring 3h forms transparent mixed solution；Take Ludox 1.88mL, pretreatment inner layer B eta molecular sieve catalytic
Agent 2g is added in transparent mixed solution, strong stirring 2h, forms gel mixed solution.
The polytetrafluoroethylcontainer container for filling gel mixed solution is placed in it is closed in reactor, in being put into calorstat, heating
To 145 DEG C, constant temperature static crystallization reacts 100h；Taking-up is placed in quenching groove, and in 10 DEG C of deionized waters 20 DEG C are quickly cooled to；Will
Mixed solution is poured in beaker, adds deionized water 1L, agitator treating 30min；3000r/min centrifugation 60min, retain heavy
Starch.Washing, centrifugation repeat 3 times.
Precipitate after washing, centrifugation is placed in roaster, 550 DEG C of roasting 5h obtain white powder.
White powder 2g after roasting, nickel nitrate 0.26g are weighed, is added together with ethanol 3.2mL in beaker, ultrasound wave dissolving
Dispersion, frequency 59KHz, jitter time 60min；40 DEG C are heated to, constant temperature stirring 6h, agitation revolution 400r/min make mixture
In volatile material fully volatilize, formed nucleocapsid structure Beta molecular sieve catalyst presomas.
Nucleocapsid structure Beta molecular sieve catalyst presomas are placed in into roaster, 500 DEG C of roasting 180min obtain nucleocapsid knot
Structure Beta molecular sieve catalysts sample 2.
Embodiment 3
Ionized water 3.1mL, tetraethyl ammonium hydroxide 40.2mL are removed, Ludox 23.3mL adds together politef to hold
In device, 40 DEG C of stirring 3h are heated to, transparent mixed solution are formed, with the speed Deca Fluohydric acid. 2.88mL of 0.1mL/min, stirring
1h, forms white gum mixed solution.
The polytetrafluoroethylcontainer container that will be equipped with white gum mixed solution is put in stainless steel cauldron, closed, is placed in perseverance
160 DEG C are heated in incubator, static crystallization 200h；Reactor is taken out, fast quickly cooling in 10 DEG C of deionized water is placed in quenching groove
But to 20 DEG C；By crystallization gel solution with 8000r/min centrifugation 20min, solid sediment is retained, be placed in vacuum drying oven
In, 100 DEG C are dried 12h, obtain white solid.
White solid product after vacuum drying is placed in roaster, 600 DEG C of roasting 300min make the template in duct
Agent is fully deviate from, and obtains white powder 6g.
White powder product 5g, ferric nitrate 0.4g are weighed, is added to together with ethanol 6mL in beaker, be placed in ultrasonic wavelength-division
Dissolving dispersion, frequency 59KHz, jitter time 60min are carried out in scattered instrument.80 DEG C of constant temperature stirring 6h are heated to afterwards, make mixture
In volatile material fully volatilize, formed inner layer B eta molecular sieve catalyst presoma.
Inner layer B eta molecular sieve catalyst presoma is placed in roaster, 500 DEG C of roasting 180min obtain inner layer B eta
Molecular sieve catalyst.
Weigh inner layer B eta molecular sieve catalyst 4g to add in 70mL diallyl dimethyl ammoniumchlorides, be stirred vigorously
1h, makes mixture fully act on, and forms mixed solution；8000r/min centrifugation 20min, retain solid sediment.By solid
Precipitate is placed in vacuum drying oven, and 100 DEG C are dried 12h, obtain white solid powder.
White solid powder 3g is weighed, Beta molecular sieve seeds 0.2g of 50～100nm of particle diameter add deionized water 50mL
In, 2h is stirred, Beta molecular sieve seeds is fully acted on white solid powder, form white mixed solution；5000r/min from
The heart separates 30min, retains solid sediment.Solid sediment is placed in evaporating dish, 100 DEG C of dryings in vacuum drying oven
12h, obtains pressed powder.
Dried pressed powder is placed in roaster, 550 DEG C of roasting 300min obtain pretreatment inner layer B eta molecule
Sieve catalyst.
Ionized water 0.67mL, tetraethyl ammonium hydroxide 0.77mL, aluminum sulfate 0.1g, sodium hydroxide 0.5g are removed, is added to
In polytetrafluoroethylcontainer container, stirring 3h forms transparent mixed solution；Take Ludox 1.32mL, pretreatment inner layer B eta molecular sieve to urge
Agent 2g, in being added to transparent mixed solution, strong stirring 2h forms gel mixed solution.
The polytetrafluoroethylcontainer container for filling gel mixed solution is placed in it is closed in reactor, in being put into calorstat, heating
To 150 DEG C, constant temperature static crystallization reacts 100h；Taking-up is placed in quenching groove, and in 10 DEG C of deionized waters 20 DEG C are quickly cooled to；Will
Mixed solution is poured in beaker, adds deionized water 1L, agitator treating 30min；3000r/min centrifugation 60min, retain heavy
Starch.Washing, centrifugation repeat 3 times.
Precipitate after washing, centrifugation is placed in roaster, 600 DEG C of roasting 5h obtain white powder.
White powder 2g after roasting, nickel nitrate 0.26g are weighed, is added together with ethanol 3.2mL in beaker, ultrasound wave dissolving
Dispersion, frequency 59KHz, jitter time 60min；It is heated to 40 DEG C of constant temperature stirring 6h, agitation revolution 400r/min, in making mixture
Volatile material fully volatilize, formed nucleocapsid structure Beta molecular sieve catalyst presomas.
Nucleocapsid structure Beta molecular sieve catalyst presomas are placed in into roaster, 500 DEG C of roasting 180min obtain nucleocapsid knot
Structure Beta molecular sieve catalysts sample 3.
Embodiment 4
Ionized water 2mL, tetraethyl ammonium hydroxide 37.2mL are removed, Ludox 21.95mL adds together politef to hold
In device, 40 DEG C of stirring 3h are heated to, transparent mixed solution are formed, with the speed Deca Fluohydric acid. 2.88mL of 0.1mL/min, stirring
1h, forms white gum mixed solution.
The polytetrafluoroethylcontainer container that will be equipped with white gum mixed solution is put in stainless steel cauldron, closed, is placed in perseverance
130 DEG C are heated in incubator, static crystallization 240h；Reactor is taken out, fast quickly cooling in 10 DEG C of deionized water is placed in quenching groove
But to 20 DEG C；By crystallization gel solution with 8000r/min centrifugation 20min, solid sediment is retained, be placed in vacuum drying oven
In, 100 DEG C are dried 12h, obtain white solid.
White solid product after vacuum drying is placed in roaster, 550 DEG C of roasting 300min make the template in duct
Agent is fully deviate from, and obtains white powder 6g.
White powder product 5g, copper nitrate 0.15g, ferric nitrate 0.15g are weighed, are added together with ethanol 7.5mL in beaker,
Being placed in ultrasound wave separating apparatus carries out dissolving dispersion, frequency 59KHz, jitter time 60min.80 DEG C of constant temperature stirrings are heated to afterwards
6h, makes the volatile material in mixture fully volatilize, and forms inner layer B eta molecular sieve catalyst presoma.
Inner layer B eta molecular sieve catalyst presoma is placed in roaster, 500 DEG C of roasting 180min obtain inner layer B eta
Molecular sieve catalyst.
Weigh inner layer B eta molecular sieve catalyst 4g to add in 60mL diallyl dimethyl ammoniumchlorides, be stirred vigorously
1h, makes mixture fully act on, and forms mixed solution；8000r/min centrifugation 20min, retain solid sediment.By solid
Precipitate is placed in vacuum drying oven, and 100 DEG C are dried 12h, obtain white solid powder.
White solid powder 3g is weighed, Beta molecular sieve seeds 0.15g of 50～100nm of particle diameter add deionized water 40mL
In, 2h is stirred, Beta molecular sieve seeds is fully acted on white solid powder, form white mixed solution；5000r/min from
The heart separates 30min, retains solid sediment.Solid sediment is placed in evaporating dish, 100 DEG C of dryings in vacuum drying oven
12h, obtains pressed powder.
Dried pressed powder is placed in roaster, 550 DEG C of roasting 300min obtain pretreatment inner layer B eta molecule
Sieve catalyst.
Ionized water 0.77mL is removed, tetraethyl ammonium hydroxide 0.96mL, aluminum sulfate 0.05g, sodium hydroxide 0.56g is added to
In polytetrafluoroethylcontainer container, stirring 3h forms transparent mixed solution；Take Ludox 1.52mL, pretreatment inner layer B eta molecular sieve to urge
Agent 2g, in being added to transparent mixed solution, strong stirring 2h forms gel mixed solution.
The polytetrafluoroethylcontainer container for filling gel mixed solution is placed in it is closed in reactor, in being put into calorstat, heating
To 145 DEG C, constant temperature static crystallization reacts 96h；Taking-up is placed in quenching groove, and in 10 DEG C of deionized waters 20 DEG C are quickly cooled to；Will
Mixed solution is poured in beaker, adds deionized water 1L, agitator treating 30min；3000r/min centrifugation 60min, retain heavy
Starch.Washing, centrifugation repeat 3 times.
Precipitate after washing, centrifugation is placed in roaster, 550 DEG C of roasting 5h obtain white powder.
White powder 2g after roasting, nickel nitrate 0.3g are weighed, is added together with ethanol 4.1mL in beaker, ultrasound wave dissolving
Dispersion, frequency 59KHz, jitter time 60min；It is heated to 40 DEG C of constant temperature stirring 6h, agitation revolution 400r/min, in making mixture
Volatile material fully volatilize, formed nucleocapsid structure Beta molecular sieve catalyst presomas.
Nucleocapsid structure Beta molecular sieve catalyst presomas are placed in into roaster, 500 DEG C of roasting 180min obtain nucleocapsid knot
Structure Beta molecular sieve catalysts sample 4.
Comparative example 1
Total silicon Beta molecular sieve white powder 2g, nickel nitrate 0.3g, copper nitrate 0.1g, ferric nitrate prepared by Example 1
0.1g, adds in beaker together with ethanol 5mL, ultrasound wave dissolving dispersion, frequency 59KHz, jitter time 60min；It is heated to 40
DEG C constant temperature stirring 6h, agitation revolution 400r/min, make the volatile material in mixture fully volatilize, and form total silicon Beta molecules
Sieve catalyst presoma.
Total silicon Beta molecular sieve catalyst presomas are placed in into roaster, 500 DEG C of roasting 180min obtain total silicon Beta point
Sub- sieve catalyst comparative sample.
Table 1 provides the nitrogen adsorption desorption data of sample 1～4 and comparative sample.Compared with comparative sample data
Find compared with analysis, the pore volume and average pore size of nucleocapsid structure Beta molecular sieves synthesized by sample 1～4 increase substantially, but compare
Surface area is slightly reduced, and illustrates that synthesized sample has very big difference with the structure of comparative sample.
Application examples 1
Separately sampled product 1～4 and comparative sample 1g, in being placed in atmospheric fixed bed micro-reactor, are passed through volume ratio for 2:1
Hydrogen and the mixed gas of nitrogen, reduction treatment 1h is carried out at 550 DEG C ± 5 DEG C to catalyst.After reduction terminates, stop being passed through
Mixed gas, with 30cm3The speed of/min is passed through nitrogen, and controlling reaction temperature is 500 DEG C ± 5 DEG C, by constant-flux pump by ethanol with
The mixed liquor of deionized water is injected in atmospheric fixed bed micro-reactor, injection rate 0.07mL/min, ethanol and deionized water
Volume ratio is 1:6, after mixed liquor is gasified, catalytic reaction hydrogen making is carried out by catalyst.
The catalytic performance of each catalyst the results are shown in Table 2.By ethanol conversion evaluation, catalyst turns wherein catalyst activity
Rate is defined as the mol ratio of the ethanol total amount of the ethanol and input reactor for reacting, and catalyst is defined as to the selectivity of product
The molar fraction of each product.
From Data Comparison in table 2, the Beta molecular sieve catalysts with nucleocapsid structure just have in lower temperature
Higher ethanol conversion and hydrogen content, and the content of its byproducts of carbon monoxide, methane and acetaldehyde is significantly lower than with monolayer
Structure Beta molecular sieve is the comparative sample of carrier.
Claims (9)
1. a kind of nucleocapsid structure Beta molecular sieves, by the inner layer B eta molecular sieve nuclear structure for accounting for 70～75wt% of the molecular sieve, and
25～30wt% outer layer Beta molecular sieves shell structure composition on the nuclear structure surface is wrapped in, wherein：
The inner layer B eta molecular sieve is loaded with accounting for the molecular sieve supported body constitution of the total silicon Beta with total silicon Beta molecular sieves as carrier
The copper and/or iron oxides of amount 3～8%, and it is connected with diallyl dimethyl ammoniumchloride base in inner layer B eta molecular sieve surface
Group；
The outer layer Beta molecular sieves by Beta molecular sieve carriers, and be carried on it is on the carrier, account for carrier quality 10～
15% nickel oxide is constituted.
2. nucleocapsid structure Beta molecular sieves according to claim 1, is characterized in that the nucleocapsid structure Beta molecular sieves
20～25 μm of crystal grain diameter.
3. the preparation method of the nucleocapsid structure Beta molecular sieves described in claim 1, comprises the following steps：
1) according to the ratio of metal oxide supported 3～8wt% of amount in inner layer B eta molecular sieve, by total silicon Beta molecular sieves with can
Dissolubility mantoquita and/or soluble ferric iron salt are added with equi-volume impregnating and are uniformly dispersed in ethanol, make ethanol fully volatilize, and form interior
Layer Beta molecular sieve precursors, 500～550 DEG C of roastings obtain inner layer B eta molecular sieve；
2）Inner layer B eta molecular sieve is immersed after fully acting in diallyl dimethyl ammoniumchloride, solid-liquid separation, solidss
After drying, it is added to the water, adds the Beta molecular sieve seeds of a small amount of 50～100nm of particle diameter, mix homogeneously, solid-liquid separation, solid
After thing is dried, 550～600 DEG C of roastings obtain the inner layer B eta molecular sieve of pretreatment；
3) ratio of 70～75wt% is accounted for according to inner layer B eta molecular sieve in nucleocapsid structure Beta molecular sieves, successively by template four
Ethyl ammonium hydroxide, inorganic silicon source, sodium hydroxide be added to the water to form transparent mixed solution, adds Ludox, pretreatment
Inner layer B eta molecular sieve, stirring forms gel mixed solution, and 130～150 DEG C of hydro-thermal static crystallizations react 72～120h, solid-liquid point
From 550～600 DEG C of roastings obtain powder solid；
4) according to the ratio of metal oxide supported 10～15wt% of amount in outer layer Beta molecular sieves, by powder solid and solubility
Nickel salt is scattered in together in ethanol solution carries out incipient impregnation, makes ethanol fully volatilize, and forms nucleocapsid structure Beta molecular sieves
Presoma, 500～550 DEG C of roastings obtain nucleocapsid structure Beta molecular sieves.
4. the preparation method of nucleocapsid structure Beta molecular sieves according to claim 3, is characterized in that described internal layer total silicon
Beta molecular sieves are to be dissolved in water to form clear solution by template tetraethyl ammonium hydroxide and Ludox, and Deca Fluohydric acid. is stirred
Mix dissolving and form white gum mixed solution, by hydro-thermal static crystallization 120 at 130～160 DEG C of white gum mixed solution～
240h；Separate solid sediment；It is dried to obtain white solid；550～600 DEG C of roastings obtain white powder silica zeolite.
5. the preparation method of nucleocapsid structure Beta molecular sieves according to claim 3, is characterized in that described soluble copper
Salt is copper nitrate, copper sulfate, copper bromide or copper chloride.
6. the preparation method of nucleocapsid structure Beta molecular sieves according to claim 3, is characterized in that described soluble iron
Salt is ferric nitrate, iron sulfate or iron chloride.
7. the preparation method of nucleocapsid structure Beta molecular sieves according to claim 3, is characterized in that described soluble nickel
Salt is nickel nitrate, nickel sulfate, nickel sulfamic acid or Nickel dichloride..
8. the preparation method of nucleocapsid structure Beta molecular sieves according to claim 3, is characterized in that the Beta molecular sieves
The addition of crystal seed accounts for the 3～6% of inner layer B eta molecular sieve quality.
9. application of the nucleocapsid structure Beta molecular sieves as hydrogen production by ethanol steam reforming catalyst described in claim 1.
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